Method and compositions for treating flexible substrates

ABSTRACT

A process for applying water-soluble chemicals to flexible substrates, e.g., textile fibers, yarns, non-woven, loomed, tufted woven and knit materials, paper and the like, which employs a readily removable carrier formulation at lower temperatures under ambient pressures consisting of preparing an aqueous-oil emulsion of the chemical and its attendant assistants, catalysts or reactive or non-reactive co-chemicals, surface active agent(s) in 1 to 35 percent by weight water and 98 to 40 percent by weight of a halogenated hydrocarbon solvent boiling between about 40* to about 165* C., applying the emulsion to a flexible substrate by dipping, immersing, flooding, doctoring, spraying or the like, introducing the so-wetted substrate into a zone filled with the vapors of the halogenated solvent which is at a temperature at or above the boiling point of the solvent of the emulsion, maintaining the substrate in said vapors for a time sufficient to remove the water and solvent from the substrate, and removing the substrate from said zone in a dry condition retaining the chemical(s) thereon or in.

[4 1 Apr. 25, 1972 [54-] METHOD AND COMPOSITIONS FOR TREATING FLEXIBLESUBSTRATES [72] Inventors: Theodore E. Tabor; Hugh A. Farber;

Thomas A. Vivian, all of Midland, Mich.

The Dow Chemical Company, Midland, Mich.

221 Filed: Sept. 29, 1969 211 Appl.No.: 862,031

[73] Assignee:

Reibnitz et al. ...1 17/161 X Hersh et al ..l 17/139.4

Primary Examiner-Murray Katz Assistant Examiner-Theodore G. DavisAtrorney-Griswold & Burdick, Glwynn R. Baker and C. E. Rehberg [57]ABSTRACT A process for applying water-soluble chemicals to flexiblesubstrates, e.g., textile fibers, yarns, non-woven, loomed, tufted wovenand knit materials, paper and the like, which employs a readilyremovable carrier formulation at lower temperatures under ambientpressures consisting of preparing an aqueousoil emulsion of the chemicaland its attendant assistants, catalysts or reactive or non-reactiveco-chemicals, surface active agent(s) in 1 to 35 percent by weight waterand 98 to 40 percent by weight of a halogenated hydrocarbon solventboiling between about 40 to about 165 C., applying the emulsion to aflexible substrate by dipping, immersing, flooding, doctoring, sprayingor the like, introducing the so-wetted substrate into a zone filled withthe vapors of the halogenated solvent which is at a temperature at orabove the boiling point of the solvent of the emulsion, maintaining thesubstrate in said vapors for a time sufficient to remove the water andsolvent from the substrate, and removing the substrate from said zone ina dry condition retaining the chemical( s) thereon or in.

5 Claims, No Drawings METHOD AND COMPOSITIONSFOR TREATING FLEXIBLESUBSTRATES BRIEF DESCRIPTION OF INVENTION wetted substrate into a zonefilled with the vapors of a halogenated solvent boiling between about 40and about 165 C. whichzone is maintained at or above the boiling pointof the solvent employed in the emulsion; maintaining the substrate insaid zone until the solvent has been removed; and finally withdrawingthe substrate from the zone in a dry condition retaining the treatingchemical.

The nature of the substrate is not critical and may be derived fromnatural or synthetic fibers and may be in the form of yarns, threads,films, sheets, woven, unwoven,;

loomed, or the like. The commonly employed fibers are or derived fromflax, cotton, wood, jute, polyamide, polyester, polyacrylate andpolyarylonitrile and mixtures thereof. These fibers may be chemicallytreated as in the case of cellulose to enable their reforming as fibers,strands, threads or films Mixtures of two or more fibers from each classmay becombined.

The halogenated hydrocarbon solvents useful in accordance with thepresent invention are those having a boiling point and resins, fireretardants and the like. Representativeof such chemicals are themethylol or alkyl ethers of methylol compounds (dimethyloldihydroxyethylene ureas), the silicones, the fluorocarbon stain andwater repellents, fluorocarbon stabilization and wrinkle resistantresins, polyethylenes, polyglycols and the inorganic salts used for fiveretardance.

DETAILED DESCRIPTION OF INVENTION EXAMPLE 1 A 100 percent cotton 80 X 80.print cloth was treated by spraying one of the compositions as setforth in the following tables, the solvent and water removed by passingthe wetted fabric through a zone of vapors of stabilized 1,1,1-trichloroethane while simultaneously passing the fabric over two heatedcans (internal steam pressure ca 60 psi). The

fabric was passed through the vapor zone at ca 10 yards per minute,residence time about 12 seconds. The fabric was dry, neither wet withmoisture of solvent upon being withdrawn from the vapor zone.

The fabric was after-cured for 5 minutes at 150 C. and the I wrinklerecovery angle measured according to AATCC 66- 1968 Monsanto WrinkleRecovery Test. Durable press was measured by AATCC 124-1967. Tensilechange and elongation change were both measured on an Instron TensileInstrument, five samples run each direction and averaged. AATCC 88C 1964 was employed to obtain crease retention values.

The control runs using only water as the formulation carrier were madein the same equipment but without the vapor zone.

like.

TABLE I Formulation percent by weight based on. total weight offormulation Dimethylol I Percent resin Wrinkle dihydroxy- Commercialsolids added on recovery ethylene Zn(NOa)2 polyethylene after dryingsolids ang Durable catalyst softener Surfactant Solvent wtJiabric wt.)degrees press 0. 6 1. 0 1. 0 81.4 6.1 279 3.3 0.6 1.0 1.0 85.4 6.4 2303.0 0.45 1.0 1.0 87.8 5.5 265 3.2 0.75 1.25 1.25 0 4.6 262 3.3 Untreatedcontrol 169 1.0

Dioctyl sodium sult'o succinate. V

The tensile change in percent and elongation change in percent are setforth in thejollowing table V 7 between about 40 and 165 C., singlespecies of halogen or TABLE 1(a) mixtures of halogen, saturated orethylenically unsaturated. 5O Tensile change, Elongation change, Thus,the chlorinated methanes, chlorinated ethanes, the Percent percentfluorinated ethanes, the mixed fluorochloro and fluorobromo warp Fm warpFm ethanes and the like. Representative of the preferred classes of --47-50 49 26 halogenated hydrocarbons falling within these classes aremethylene chloride, chloroform, carbon tetrachloride, 1,1,1- 5 :g- :gfig :22 trichloroethane, trichloroethylene, perchloroethylene;dibromotetrachloroethane, tetrachlorodifluoroethane,dichlorotetrafluoroethane, trichlorotrifluoroethane and the EXAMPLE 2 Inanother series of experiments, a /35 polyester cotton broadclothshirting fabric was treated in the same manner as set forth in Example 1using the formulations set forth in Table II. The durable press ratingand crease resistance were measured and are set forth in the Table.

TABLE II Percent by weight Catalyst (15% based Durable on resin Percentpress Crease S D.P. resin Water solids) Softener Surfactant Solventadded on rating resistance DP+CR 11 0. 9 1. 0 1. 0 Balance 5. 0 3. 5 4.2 717 14 1. 2 1. 0 1. 0 Balance. 8. 2 3. 3 3. 8 7. 1 16 1. 5 1. 0 1. 0Balance.-. 10. 3 3. 5 4. 4 7. 9 Del. 1.125 1.0 4.9 3.4 4.1 7.5 Bal.1.47 1. 0 6. 0 3. 6 4. 4 7. 4 Bal. 1. 8 1. 7. 6 3. 6 3. 8 7. 4 Control,untreated 2.5 2. 6 5. 1

A durable press resin (dimethylol dihydroxyethylene urea) and either asilicone water repellent resin or a fluorocarbon water and stainrepellent resin were applied from a formulation within the teaching ofthe present invention to a 50/50 polyester-cotton poplin fabric. Thefabric was wetted with formulation to about 50% wet pick-up in aButterworth 15 inch Laboratory Padder, 1 dip l nip. The results of theseoperations are set forth below.

The formulations employed were:

A. 10% by weight dimethylol dihydroxyethylene urea (DMDHEU), 1.5% Zn(NO1% polyethylene, 2% DC TABLE V 1' Removed Resin by Solvent ApplicationWash Cotton Aqueous Emulsion 3 Polyester Aqueous 68 Emulsion 61Polyester-Cotton Aqueous 16 Emulsion 25 Hand of the washed fabric wassofter than non-solvent washed controls.

polyester-cotton batiste. The washing was conducted for 20 minutes in1,1 ,l,-trichloroethane containing 0.0045 percent by weightdioctylsodiumsulfosuecinate, rinsed twice for 10 minutes in 1,1,l-trichloroethane and air dried. The amount of resin lost is recordedbelow:

l 109 silicone, 15.8% water and 69.7% 1,1,1- 1 5 EXAMPLE 6trichloroethane. B. 10% (DMDl-lEU) A paste was made by mechanicallymixing 25 percent of a 1.5% Zn(NOah commercial carpet backsi'zingcompound and 75 percent 1% Polyethylene l,l,l-trichloroethane. Thecarpet backsizing compound used 2% DC 1172 silicone was 65 percentsolids in water. The solids portion consists of 0.1% DC catalyst XY-168100 parts styrene-butadiene latex and 350 parts calcium car- 15.1% 11 0bonate. An even coat of the above paste was applied to a piece 703% 1,1,l-Trichloroethane of carpeting 4 inches by 3 inches using a brush. lncommercial C. 10% DMDHEU applications, such materials are generallyapplied by roll coat 1.5% Zn( N0 followed by a doctor blade. The initialweight increase on the 1% Polyethylene carpet sample was approximately140 percent. The treated 0.63% Fluorocarbon PC 208 carpet sample wasthen dried by laying it on a hot metal surl5.8% Water face at 250F. withthe pile side contacting the metal surface. 71.1% 1,1 ,l-TrichloroethaneThe sample dried quite rapidly and was weighed periodically TABLE IIIPercent add-on Spray rating Oil rating resin wt./ Formulatlon fabrlc wt.WRA Inltlal 1 Wash 6 Washes Initial 1 Wash 7.9 298 100 90 1 1 7.1 311100 100 80 0 7.7 300 100 80 5 4 Untreated 217 O 0 1 1 EXAMPLE 4 40during the drying process. The sample was dry after approximately 25minutes as there was little additional weight loss In another Series Ofexperiments. the efkct of conditioning after this period. The sampleweight at this point indicated a of the fabric with Steam after curingwas determinedbacksizing add-on of approximately 25 percent on theinitial 100 Percent 80 X 80 cotton Print cloth was Sprayed with a weightof the sample. This technique gave a good uniform formulation consistingof: coating on the carpet sample.

8% N,N'-bis methox meth luron LN znclz Y y We claim. 7 32g; ffrj'fg l. Aprocess for the application of water-solubledurable press resins, waterrepellent resins and chemicals, stain repel- The vetted fabfic'was Thefabric, found to have lent chemicals, fiber stabilization chemicals,dyes, softeners, about a P add'Oh of resin was Steamed at lubricants,soil release chemicals, finishing chemicals and mosphel'ic Pressure,Cured at for 5 minutes- The resins on fire retardant, or mixturesthereof to a flexible sub- "sults of the are set frth below: strate ofnatural and synthetic fibers and yarns, threads, films sheets thereofwoven, unwoven or loomed which comprises: TABLE IV applying thechemicals to the flexible substrate from an aqueous emulsion carrierwhich contains 1 to 35 percent by weight Steaming Time (Min.) WRA waterbased on the total weight of the emulsion, 98 to 40 per- 3-3 :2; cent byweight of a halogenated hydrocarbon solvent having a 263 boiling pointbetween about 40 and 165 C., the treating 3 0 no chemicals being presentin from 0.2 to 15 percent by weight; 157 introducing the wettedsubstrate into a zone filled with vapors of a halogenated solvent havinga boiling point between about 40 and 165 C. which is at or above theboiling point of the EXAMPLE 5 55 halogenated hydrocarbon solventemployed in the emulsion; maintaining the substrate in said zone untilthe halogenated In another series of experiments, the effect of solventwashhydrocarbon solvent and water are removed f o h b- S Prior to curewas determihed' The nature of the treating strate; and, withdrawing thesubstrate from the zone free of formulation and treatment technique wasas set forth in Examwater and halogenated hydrocarbon solverm P 1 gcotton P cloth, Polyttstef Plain Weave and 2. The process of claim 1wherein said flexible substrate is a textile fabric, said chemicals area durable press resin of the class methylol and alkyl ethers of methylolcompounds, a catalyst for said resin and said halogenated hydrocarbon isthe same solvent as that employed to fill the vapor zone.

3. The method of claim 2 wherein the substrate is steamed at atmosphericpressure for from 0.5 to 4 minutes, then heated dihydroxyethylene ureaand the catalyst is Zn(NO at from 150 160 C. to cure the resin. 5. Theprocess of claim 2 wherein said resin is N,N'-

4. The process of claim 2 wherein said resin is dimethylolbis(methoxymethyl)uron and the catalyst is zinc chloride.

2. The process of claim 1 wherein said flexible substrate is a textilefabric, said chemicals are a durable press resin of the class methyloland alkyl ethers of methylol compounds, a catalyst for said resin andsaid halogenated hydrocarbon is the same solvent as that employed tofill the vapor zone.
 3. The method of claim 2 wherein the substrate issteamed at atmospheric pressure for from 0.5 to 4 minutes, then heatedat from 150* - 160* C. to cure the resin.
 4. The process of claim 2wherein said resin is dimethylol dihydroxyethylene urea and the catalystis Zn(NO3)2.
 5. The process of claim 2 wherein said resin isN,N''-bis(methoxymethyl)uron and the catalyst is zinc chloride.